Degradation of N,N'-dibutylurea (DBU) in soils treated with only DBU and DBU-fortified benlate fungicides

N,N'-dibutylurea (DBU) is a breakdown product of benomyl [methyl 1-(butylcarbamoyl)-2-benzimidazole carbamate], the active ingredient in Benlate fungicides, and has been proposed to cause crop damage after the use of Benlate 50 DF fungicide (DuPont, Wilmington, DE). Our research focused on DBU persistence after application into soil. We assessed DBU persistence on direct application of DBU (carbonyl-(14)C) at two concentrations (0.08 and 0.8 microg DBU kg(-1)) to seven soils and two potting mixes in soil microcosms incubated at various combinations of soil water potential (-0.03 or -0.1 MPa) and temperature (23, 33, 44 degrees C). For two soils at a subset of treatment variables we assessed DBU persistence in the presence of Benlate DF and SP fungicide formulations. Parent compounds, metabolites, and (14)CO(2) were tracked using chromatographic analysis with radioassay and UV detection, liquid scintillation counting, and post-extraction oxidation of the soil. DBU degradation was primarily microbial and for most soil-treatment combinations, half-lives were less than 2 wk. DBU degradation was retarded at the lower soil water potential and enhanced at 33 degrees C. In the presence of the formulation, DBU degradation was slower for one soil type. The longest half-life observed in any case was less than 7 wk; therefore, long-term persistence of DBU applied to soils through a Benlate application is very unlikely.     

Statistical analysis of heavy metals in Cerastoderma edule glaucum and Venerupis aurea laeta from Ganzirri Lake, Messina (Italy)

Our study was carried out on two species of clams, Venerupis aurea laeta and Cerastoderma edule glaucum, from Ganzirri Lake considered as “environmental biomarkers” for their changes in physiology, morphology or distribution under the influence of substances in the environment. The aim of the present study was to conduct a statistical analysis on Venerupis and Cerastoderma to investigate the difference between the two autochthonous clams according to the presence of metals, and to link metal concentrations to the reproductive cycle of clam during 2009–2010. Metal analysis was carried out with inductively coupled plasma mass spectrometry (ICP-MS). Accuracy and precision were assessed by analyzing the certified standard matrix: mussel tissue NIST SRM 2976. The multivariate analysis was made using the SPSS 13.0 software package for Windows (SPSS Inc., Chicago, IL). In this study, the concentrations of some metals found in clam tissues showed seasonal cycles with higher values in summer than in winter. The significances of metal concentrations differences between Venerupis and Cerastoderma samples were estimated with Mann–Whitney U-test. The concentrations of Ag, As, Cd, Mn, Se and Zn show a significant p-level that suggests a difference between the two group samples. Statistical analysis showed that the link of metal concentrations to the reproductive cycles of Venerupis and Cerastoderma was not evident.     

Levels and congener pattern of polychlorinated biphenyl and organochlorine pesticide residues in bluefin tuna (Thunnus thynnus) from the Straits of Messina (Sicily, Italy)

The aim of this study is to assess the accumulation of OCs and PCBs in Thunnus thynnus and to elucidate the suitability of this species as a bioindicator for monitoring contaminations of these compounds in the marine ecosystems of the Straits of Messina. This investigation was conducted on fat, liver and muscle samples of 14 T. thynnus collected during April 2004. Quantitative determination of OCs and PCBs in the various samples examined has been carried out using GC-ECD and GC-MS. The results obtained show the presence of low concentrations of p,p'-DDE and PCB congeners (138, 153 and 180) in all fat, liver and muscle samples caught in the Straits of Messina. Concentrations of p,p'-DDE and PCB congeners (138, 153 and 180) in all the samples examined were below MRLs (CE n. 97/41, 1999/65 and 1999/71).     

Autochthonous clams monitoring of Ganzirri Lake (Sicily)

Two autochthonous clams, Venerupis aurea laeta and Cerastoderma edule/glaucum, collected for a period of 1 year, from May 2007 to January 2008, were studied in the Cape Peloro lagoon. On the samples, it was evaluated the presence of pathogenic microorganisms and proteins, lipids and yield edible part were determined. It was evaluated the concentration of mineral elements (Cd, Cu, Mn, Se, Pb, Zn) and organic contaminants (∑DDT and PCBs). Salmonella is never present in any sample. Total and faecal coliform values have always been under law limits for alive bivalves mussels production and sale. Zn, Cu, Cd and Pb levels were found in clams where they are slightly lower too. Both species do not show significant changes for Mn and Se. DDT and PCBs traces were discovered in Ganzirri Lake’ samples, but in all observed cases, they were below law limits. As a result of all these observations, it is clear that, in recent years, the bivalve’s use of Ganzirri Lake does not denote toxicological risk to human health.     

Estimation of Efficiency of Processing Soil Samples for Pesticide Residues Analysis

The efficiency of four sample processing methods was tested with eight different types of soils representing the major proportion of cultivated soils. The principle of sampling constant was applied for characterizing the efficiency of the procedures and testing the well-mixed status of the prepared soil. The test material was 14C-labeled atrazine that enabled keeping the random error of analyses ≤ about 1%. Adding water to the soil proved to be the most efficient and generally applicable procedure resulting in about 6% relative sample processing uncertainty for 20 g test portions. The expected error is inversely proportional to the mass of test portion. Smashing and manual mixing of soil resulted in about four times higher uncertainty than mixing with water. Grinding of soil is applicable for dry soils only, but the test procedure applied was not suitable for estimating a typical uncertainty of processing dry soil samples. Adding dry ice did not improve the efficiency of sample processing.     

Organochlorine pesticides and polychlorinated biphenyl residues in reared and wild Dicentrarchus labrax from the Mediterranean Sea (Sicily, Italy)

The aim of this research was to compare the levels of organochlorine pesticides and PCBs in samples of Dicentrarchus labrax living in the Straits of Messina with samples cultivated in cages in the Mediterranean Sea. Muscles and liver tissues sampled over the months, within the same year, were analyzed. The quantitative determination of the organochlorine compounds was performed by GC-ECD and confirmed with GC–MS. The results showed that the concentrations of DDTs in muscles and livers as such of reared sea bass were in the range 0.2–1.3 μg/kg and 9.6 –48.4 μg/kg, respectively. In wild fish the concentrations of DDTs were very much lower: 0.1 μg/kg in muscles, 5.1–9.0 μg/kg in livers. Total PCBs levels were higher in cultivated sea bass than in wild fish; the concentration ranges were 5.3–59.7 μg/kg and 74.4–267.4 μg/kg in muscle and liver of reared samples, respectively, and 1.1–1.5 μg/kg and 63.2–109.4 μg/kg in muscle and liver of wild samples, respectively.     

Speciation of inorganic arsenic in coastal seawater from Ionian and Tyrrhenian Seas (Sicily, Italy) using derivative anodic stripping chronopotentiometry

The purpose of this paper was to use derivative anodic stripping chronopotentiometry (dASCP) as a sensitive and accurate technique, to determine the concentrations of dissolved As (III) and As (V) in coastal seawater samples from the Straits of Messina, the Ionian and the Tyrrhenian seas, and to investigate the relationship between the anthropogenic activities on the coastal areas and the concentration of dissolved inorganic arsenic in seawaters. The obtained data indicated that As (V) was the most abundant species, with concentration ranging from 26.7 to 307 nM, whereas As (III) levels were lower than 48 nM in all the samples. In particular, As (III) and As (V) levels significantly decreased from high to low anthropogenic activities zones (p < 0.00001, ANOVA), with the reference samples, from a wildlife reserve, showing the lowest values. Furthermore it was observed that human activities influenced inorganic arsenic speciation, since the zones that received high human input presented the highest As(V)/As (III) ratio.     

Testing instrumental and downscaled reanalysis time series for temperature trends in NE of Spain in the last century

In the context of climatic temperature studies, more often than not a time series is affected by artificial inhomogeneities. To overcome such limitation, we propose a new simple methodology in which promising results point not only toward the detection of unknown inhomogeneous periods but also toward the possibility of reconstructing the uncertain portion of the series. It is based on a parsimonious statistical downscaling (Multiple Linear Regression) of the large-scale 20CR reanalysis data. This method is successfully applied upon two long-range temperature series from a couple of centennial observatories (Ebre and Fabra, NE of Spain) which do not have nearby suitable temperature series to compare with. Results of trend analysis point to a clear signal of warming, with a larger rate of increase for the maximum temperature (respect to the minimum one), for the more recent decades (respect to the whole available period), and for the original series (respect to the reconstructed ones).